TW201139496A - Halogen-free flame-retardant epoxy resin composition, and prepreg and printed wiring board using the same - Google Patents

Abstract

A halogen-free flame-retardant epoxy resin composition is provided, which includes (a) an epoxy resin, (b) a styrene-maleic anhydride copolymer used as a curing agent, (c) poly(1, 3-phenylene methylphosphonate) used asa flame retardant, (d) a curing accelerator, and (e) an inorganic filler.

Description

201139496 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to an epoxy resin composition, particularly a kind of elemental element = flammability Wei Yi group secret and the handle of the material handle ah) and printing = The cutting plate 4 cuts the prepreg or the drilling of the printed circuit board is difficult, and the amount of dust discharged by the glue I is significantly reduced. [Prior Art] With the consideration of the flame retardancy of electronic materials, conventional electronic components will utilize the desert

Raw materials to increase its effect, * the industry's awareness of the rise of misunderstanding, electronic component materials also began to require no environmentally friendly materials, such as for the manufacture of printed circuit boards, Lin Bu has changed from fine epoxy to nitrogen Or filled with epoxy resin. Generally, the most important substrate of a printed circuit board is a copper-coated substrate (copper = ad l^ninate 'CCL), and the copper-clad-coated substrate is made of a reinforcing material such as fiber paper or glass cloth. The substrate is impregnated with phenolic resin or epoxy resin, and is baked, cut, laminated, and hot pressed to form a laminated board, and then the copper foil is coated on one or both sides of the laminated board, and heated and pressurized. It is produced by forming under conditions. With the evolution of technology, printed circuit board production is complicated, and the demand for prepreg or laminated board products that can improve heat resistance or glass transition temperature (Tg) is becoming more and more urgent, and in order to improve the glass transition temperature of prepreg, in impregnating resin In the formulation, the conventional Lingjun epoxy resin will be further matched with Styrene-Maleic anhydride Copolymer (SMA), for example, Taiwan Patent No. 455613 to improve the phenolic epoxy resin. The glass transition temperature of the prepreg's, however, such high glass transition temperature products are susceptible to some drawbacks of 'needs further improvement' where, for example, brittleness becomes higher, and the prepreg is cut or the printed circuit board is drilled. During the processing, it is easy to produce the problem that the rubber dust 201139496 or the filling powder falls, so it is easy to cause pollution for the process or the product. 'In order to solve the problem that the substrate is broken or the filler powder falls during processing such as cutting, drilling, etc., one method is to further add a polymer thermoplastic resin (molecular weight greater than 5000) to the impregnated resin, for example, Carboxyl-terminated butadiene acrylonitrile (CTBN) or phenoxy resin (Phenoxy), etc., to improve the generation of dust or dust, and at the same time the toughness of the prepreg is also improved. However, the addition of such a polymer thermoplastic resin significantly reduces the substrate_dip solderability, and has a bad influence on Wei New, such as the factor (4), the dielectric constant (Dk), etc., and also causes the copper foil pair. The adhesion of the substrate is reduced. How to solve the problem of easy brittleness caused by the use of stupid ethylene·maleic anhydride as a hard resin in the process of processing, and avoiding the problems caused by the addition of high-molecular heat saplings in the sputum It becomes a research subject of the present invention. SUMMARY OF THE INVENTION The purpose of the present invention is to provide a halogen-free barrier epoxy group, which can produce a prepreg having good resistance to immersion and mechanical insulation. Material or printed circuit board, and drilled into the inspection material or _ (four) road board for the accumulation of board is also secondary = grid title can be improved more 'at the same time, the layer +1 series is providing a prepreg, It is obtained by preparing a composition varnish in a solvent epoxy tree r: two (10) main non-form epoxy resin composition, and then impregnating a reinforcing material such as a glass fabric with a peach resin composition varnish. Baked and prepared. [S] 4 201139496 A further object of the invention is to provide a method for providing the following method, the method comprising: applying a certain number of layers of the above-mentioned functions to at least one of the at least one side of the prepreg The outer layer laminated metal (4) ^ metal coated laminated board 'and pressurized and heat-formed the metal coated laminated board, and then removes the metal falling of the above-mentioned metal coated laminated board table, a certain circuit pattern In this way, a printed circuit board can be obtained. ^

In order to achieve the above objectives, the present invention provides an epoxy resin composition comprising (8) a halogen-free epoxy resin; (b) a benzoic acid maleic anhydride copolymer as a hard (like methyl benzoate) (p〇 Ly (1,3_phenyiene ^ 'methylph〇Sph〇nate), referred to as PMP) as a flame retardant; (4) hardening and (e) inorganic filler, wherein polymethyl squaric acid u • phenyl vinegar and benzene The ratio of the maleic anhydride copolymer is 2〇: U4〇: i by weight, and it is preferred that the present invention uses a styrene-maleic anhydride copolymer as a hardener and a polybasic, I,3· Based on the purpose of blocking the paste, and the above two depending on the specific, epoxy resin cross-linking reaction, can be high-glass complementary temperature of the epoxy, the composite material 'especially made of the job, the printing road plate with Wei Good resistance to dip soldering, mechanical, electrical and electrical properties (such as Dk, Df), while avoiding the brittleness problem caused by the use of styrene-maleic anhydride copolymer as a resin hardener. The above and other objects, features, and advantages of the present invention will become more apparent. [Embodiment] The epoxy resin composition of the present invention comprises: (8) 100 parts by weight of a halogen-free epoxy resin; (b) 10.0 to 2α parts by weight of a styrene-maleic anhydride copolymer as a hardener, (c) 25.0 to 7 〇. 〇 by weight of bismuth methyl methacrylate, 3 _ stupyl ester as a flame retardant; parts by weight of a hardening accelerator; and (e) 5 〇i 201139496 30.0 heavy smashed inorganic The filler, each component by weight is based on 1 (8) parts by weight of a halogen-free epoxy resin, and the ratio of polymethyl phosphonium phosphate, 3-phenylene ester and styrene-maleic anhydride copolymer is by weight. It is calculated as 2 〇··丨 to 4.0: and preferably 2.7: 1.0. The halogen-free flame-retardant epoxy resin composition of the present invention is a halogen-free epoxy resin, including (1) Nitrogen-containing epoxy resin, such as Benzoxazine (BZ) / phenolic epoxy resin copolymer or triazine ring-containing knot, secret Wei fine; and (2) containing _ lipid, scaly a secret type epoxy resin which is a side chain type phenol-containing epoxy resin, and the above resins may be used singly or in combination at the same time. In the specific embodiment, the phenolic epoxy resin is an o-Cresol Novolac Epoxy Resin (CNE) (label ccp 330) and the organic ring Squamous squamous compounds, for example, 9-dihydroxanthene-1-indene-1 〇-oxide (9,10-Dihy dro-9-oxa·1 〇_ph〇sphaphenanthrene_ 10- 〇=de, abbreviated as D0P0 'Factory κ〇1〇η5138), introduced into the structure of the o-cresol novolac epoxy resin, to form a DQPO-containing phthalate epoxy resin (which is a side chain type) Phosphorus-containing phenolic epoxy resin), and D〇p〇 knot

The component (b) of the halogen-free flame-retardant epoxy resin composition of the present invention is a hardener, for example, a styrene-maleic anhydride copolymer (label Sart0mer EF40), which can further mix other hardeners such as primary amines. Hardener, such as dicyandi

201139496 diphenyl sulfone, referred to as DDS). The styrene-maleic acid copolymer used may have a molecular weight of between 1400 and 50,000, and its structural formula is as follows:

' HICIC η where ' m is an integer from 1 to 6, and n is an integer from 2 to 12. The component (c) in the halogen-free flame-retardant epoxy resin composition of the present invention is a flame retardant, for example, poly(methyl benzoate) 1,3-phenylene. The molecular weight of the poly(1,3-methylphenyl) 1,3-phenylene ester used is less than 1 〇〇〇, and its structural formula is as follows:

Where 'm = 0 or 1, n = 〇 or 1, p is an integer. The ratio of the 1,3-phenylene group of the present invention to the styrene-maleic anhydride copolymer is from 2.0:1 to 4.0:1 by weight, and preferably 2 7:1〇. . The component (d) in the halogen-free flame-retardant epoxy resin composition of the present invention is a hardening accelerator' including 2-Methyl-Imidazole (2MI) and ethyl-4-mercapto σ sits (2-Ethyl-4-Methyl-Imidazole, 2E4MI), 2-phenylimidazole (2 small 1^1^1-11^(^〇16, 2?1), wind: ^-dioxin Benzyldimethylamine (BDMA) and dimercaptoalkylamine, and the above-mentioned hardening accelerator may be used alone or in combination of two or more. The hardening accelerator accelerates the hardening time of the prepreg. Additive component in epoxy resin composition (e) Inorganic filler, including calcium carbonate (CaC03), talc (Mg3Si4〇iQ(OH)2), broken glass powder, II201139496 Tongling, mica, KOH and Al2O3, and the above inorganic filler may be used singly or in combination of two or more kinds. The inorganic octagonal resin 9) imparts workability, flame retardancy, heat resistance or moisture resistance to the epoxy resin. Sex and other characteristics.

The solvent for the halogen-free flame-retardant epoxy resin composition varnish of the present invention includes acetone (ACetone), methyl ethyl ketone (MEK), propylene glycol methyl ether (pM), cyclohexanone, and propyl alcohol methyl ether acetate (PlOPylene Glycol Methyiaher Acetate, PMA) and Dimethyl Formamide (DMF), and the above solvent J may be used alone or in combination of two or more. Based on the halogen-free epoxy resin of 1 曰 罝 , , , , , , 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 溶剂 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧(4) It is prepared by uniformly mixing with a mixer. Thereafter, a halogen-free anti-corrosive resin composition varnish is prepared by dissolving or dispersing the epoxy resin test substance in a solvent to sub-adjust the viscosity of the epoxy resin. "' Next, impregnate the varnish prepared above in the reinforcing material used to form the prepreg, and heat it in the dryer with (9) ~ gift c 2~ reaction, thereby composing the gar. It is also possible to use a glass fiber cloth such as bismuth, in addition to the short-staple tissue paper such as weibu, the woven cloth, the organic fiber, and the laminated layer in the layer of the dipping material, which is laminated and heated to form. Obtaining copper: called Zhang Tongbo' and pressing it into a method such as pressing, so that the copper is laminated. Then, by the copper box on the surface of the laminated board behind the side, only the part of the pattern forming the circuit 201139496 remains and is removed. Other parts are used to form a circuit pattern, so that a printed circuit board having a circuit can be obtained. The embodiments provided below are merely illustrative of the technical means of the present invention and are not intended to limit the technical scope of the present invention. Comparative Examples 1 to 2 are 100 parts by weight of the toothless epoxy resin, and the other components are expressed in relative parts by weight. By way of example, 100 parts by weight of a phosphorus-containing (DOPO) ortho-phenolic epoxy resin, 15 parts by weight of styrene-maleic anhydride copolymer 40 parts by weight of 1,3-phenylene phenyl benzoate, 0.5 parts by weight of 2-mercaptoimidazole and 15 parts by weight of cerium oxide, mixed at room temperature for 60 minutes using a stirrer, and then added 3 〇 Parts by weight of acetophenone. The above materials were stirred at room temperature for 12 minutes to form a halogen-free flame-retardant epoxy resin composition varnish. Example 2 〇〇 parts by weight of phosphorus (DOPO) An o-phenolic epoxy resin, 15 parts by weight of a styrene-maleic anhydride copolymer, 30 parts by weight of a poly(methyl sulfonate) 1,3-styl ester, 0.5 parts by weight of 2-mercaptoimidazole, and 15 parts by weight of cerium oxide, mixed with a stirrer at room temperature for 6 minutes, and then added 3 parts by weight of methyl ethyl ketone. The above materials were stirred at room temperature for 12 minutes to form a halogen-free flame retardant. Epoxy resin composition varnish. Example 3 100 parts by weight of ortho-type epoxy resin containing sarcophagus (DOPO), 15 parts by weight of styrene malay bribe (four), 6G parts by weight 1,3_Standing base, 0.5 parts by weight of 2·曱 base flavor saliva and 15 parts by weight of dioxide dioxide, stir at room temperature The mixture was mixed for 6 minutes, and then 3 parts by weight of methyl b. was added. After the above materials were allowed to stand at room temperature for -12 seconds, a non-halogen flame-retardant epoxy resin composition varnish was formed. 100 parts by weight of an o-cresol novolac epoxy resin containing phosphorus (D〇p〇), a stupid ethylene-maleic anhydride copolymer of Toray Dong, 10 parts by weight of a diaminodiphenyl group (DDS), 54 parts by weight of polymethyl silicate 1,3-phenylene vinegar, 0.5 parts by weight of 2 I imidazole, and 15 parts by weight of bismuth ruthenium hydride, stirred at room temperature for 60 minutes, and then added 3 parts by weight of methyl ethyl ketone. The above materials were stirred at a temperature of 12 G minutes to form a varnish-free epoxy resin composition varnish. Embodiment 5: 100 parts by weight of a phosphorus-containing (D0P0) ortho-novolak type epoxy resin, a 1 gram weight-wound stupid ethylene-maleic anhydride copolymer, and 27 parts by weight of a polymethyl-acid acid 1,3_ The stearyl ester, 0.25 parts by weight of 2-methylimidazole, and 15 parts by weight of the silica dioxide were mixed at room temperature for 60 minutes using a stirrer, and then 30 parts by weight of acetophenone was added. After the above materials were stirred at room temperature for 12 minutes, a fang-free flame-retardant epoxy resin composition varnish was formed. Example 6 100 parts by weight of a phosphorus-containing (DOPO) ortho-cresol type epoxy resin, 1 part by weight of a stupid ethylene-maleic anhydride copolymer, and 5 parts by weight of a diamine-based diphenyl-based hard (DDS) 30 parts by weight of polymethyl phosphonium phosphate, 3-phenylene ester, 5 parts by weight of 2-mercaptoimidazole and 15 parts by weight of cerium oxide, mixed at room temperature for 60 minutes using a stirrer, and then 3 parts by weight of methyl ethyl ketone was added. After the above materials were stirred at room temperature for 120 minutes, a fang-free flame-retardant epoxy resin composition varnish was formed. Comparative Example 1 100 parts by weight of an o-cresol novolac epoxy resin containing phosphorus (DOPO), 15 201139496

100 parts by weight of o-f _ type epoxy resin containing ruthenium 30PQ), 15 parts by weight of styrene maleic anhydride silk, 7 g parts by weight of polyfluorenyl 1,3-phenylene, 0.5 parts by weight 2 曱 味 味 以及 and 15 parts by weight of styrene-maleic anhydride copolymer, 〇 5 heavy at room temperature using stirring H mixed 6G minutes, plus 3 〇 weight of ketone. After the above materials were stirred at room temperature for 12 minutes, cerium oxide was formed in the chamber. Halogen-free flame retardant epoxy resin composition varnish. The halogen-free flame-retardant epoxy resin composition varnish prepared in Examples 1 to 6 and Comparative Examples 1 to 2 was coated on 7628 (R/C: 43%) glass fiber cloth by a roll coater, followed by coating on a 7628 (R/C: 43%) glass fiber cloth. This was placed in a dryer and dried by heating at 180 C for 2 to 10 minutes to prepare a semi-hardened prepreg. Then, four prepregs were laminated, and a copper foil of loz was laminated on the outermost layers on both sides. Then, it is press-heated and pressed, thereby obtaining a copper foil-clad laminate, wherein the conditions of pressure heating are as follows: 2.0 〇C/min liter; phoenix speed ' reaches 180 C' and 180 ° C, all 15kg / cm2 (initial pressure 8kg / cm2) under pressure heating for 60 minutes, and made a copper-coated laminated board. Then, by the subtractive method such as etching, the copper foil coated on the surface of the laminated board has only the portion where the circuit pattern is formed, and the other portions are removed, thereby forming a circuit pattern. Accordingly, a printed circuit board having a circuit on the surface layer can be obtained. The dip solderability of the prepared copper foil coated laminated board (S〇lder

Floating), peeling strength, glass transition temperature (Tg), thermal decomposition temperature (Tg (5%)), flame retardancy, 201139496 blade edge, dielectric constant, dissipation factor and The amount of the drop was measured, and the flame retardant epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 2 and the evaluation results thereof are shown in Table 1.

12 201139496 Μ Λ

Comparison composition two 〇ι"Ή yr\ Ο ο ο evaluation results comparison example II I: CN | 150.4 | 352.1 1 ν-0 1 1 4.85 | 0.011 <0.01 Comparative example one ο ο Comparative example one >10 οό 155.3 342.9 V-0 4.38 0.010 〇Embodiment 〇ο ο m in ο to 1 _ Example Six 〇 oo 150.5 353.9 V-0 4.54 0.013 <0.01 Example 〇 » » Η ο 0.25实施 Example 5〇〇<o 00 144.5 349.3 V-0 4.53 0.013 <0.01 Example 4〇ο (Ν ο Ο I 实施 Example 4 m oo 156.5 358.1 V-0 4.57 0.011 0.011 Example 3〇τ· ^ ο s in ο ΙΟ ι i Example 3 IT) 00 151.3 351.2 V-0 4.57 0.013 <0.01 Example 2 〇 yr ο ο ο m ο Example 2 > 10 CN oo 152.3 358.2 o $ 4.48 0.011 < 0.01 Example 1 〇Η w Ή ο ο ο 〇 cn | Example 1| |_ >10_J 〇\ | 155.3 | 355.4 1 v-° 1 1 4·51 1 1 0.011 I <0.01 in 100 parts by weight Halogen-free epoxy resin as the benchmark, the other components are relative parts by weight (PHR) phosphorus-containing (DOPO) o-cresol novolac epoxy resin SMA DD S PMP 2MI cerium oxide MEK unit min lb/in 1 UL94 relative toughness too condition 288 °C DMA TGA flame resistance grade manual judgment Dk (lGHz) Df (lGHz) C • wm J-inch halogen-free epoxy resin hardener flame retardant Agent accelerator filler solution characteristics dip soldering tear strength (loz) Tg (5% weight loss) flame retardancy toughness|dielectric constant|dissipation factor drop amount 201139496 property test: [cluster solderability test] After the dried laminated sheets were immersed in a solder bath at 288 ° C for a certain period of time, it was observed whether defects were present, for example, by delamination or expansion of the laminated sheets. [Tear strength test] The tear strength refers to the adhesion of the copper foil to the substrate, and is usually torn vertically from the surface of the copper foil with a width of two inches per inch (25.4 mm), with the required strength. To express the strength of adhesion. MIL-P-55110E specifies a 1 oz steel box substrate with a pass standard of 4 lb/in. [Glass Transfer Temperature Test] The glass transfer temperature (Tg) was measured using a dynamic mechanical analyzer (DMA). The test specification for the glass transfer temperature is the IPC-TM-650.2.4.25C and 24C test methods of The Institute for Interconnecting and Packaging Electronic Circuits (IPC). [Thermal decomposition temperature test] The temperature at which the mass was reduced by 5 ° / 〇 was measured by a thermogravimetric analyzer (TGA) as the thermal decomposition temperature. [Flameability test] Using the UL94 V: vertical burning test method, the laminated plate is fixed in a vertical position, and burned with a Bunsen burner. The self-ignition extinguishing and combustion-supporting characteristics are compared, and the result is classified into UL94V-0 (the most Good) to UL94V_2 flame resistance rating. [Toughness test] Lay the laminated board on the flat fixture, and use the cross-shaped metal fixture to vertically contact the surface of the laminated board, and then apply vertical pressure. Then remove the cross fixture and observe the ten sub-type on the substrate. Traces, the surface of the laminate is examined. If no white crease occurs, it is judged to be good, and the white streaks are generally normal, and cracks or breaks are bad. 201139496 [Dielectric Constant and Dissipation Factor Measurement] The dielectric constant (Dk) and the dissipation factor (Df) are calculated at the operating frequency i gHz according to the ASTM D150 specification. [Dropage test] After weighing 4 inch squares of laminated board, press the punch to form a 3.192 inch square circle. The weight formed by the stamping is removed and the weight loss is the dust. The amount of drop. The low molecular weight polymethyl sulphate used in the invention has the advantages that the 3-phenylene ester is prepared in the process: the polydecylphosphoric acid having a molecular weight of less than 1 13 is in a liquid state. It is easy to prepare and does not affect the hardening reaction time of the stupid ethylene·maleic anhydride copolymer and the halogen-free epoxy resin. The resin composition varnish is easily blended. The conditions of Example 1 are optimal. Examples 2 and 3 respectively show the ratio of poly(fluorenylphosphoric acid) 1,3-phenylene styrene to styrene-maleic anhydride copolymer by weight of 2.0.1 and 4.0:1. Examples IV and 5 show that the ratio of the 1,3 -phenylene ester of polymethylphosphoric acid to the styrene-maleic anhydride copolymer is 2.7:1 by weight, and the higher amount and the lower amount are respectively used. An embodiment of the styrene-maleic anhydride copolymer, wherein the hardeners used in the fourth and sixth embodiments are not a single styrene-maleic anhydride copolymer component but a styrene-maleic anhydride component. A composite hardener composed of a copolymer and a diaminodiphenyl sulfone is prepared in combination with polymethyl phosphonium phosphate and 3-phenylene ester. As can be seen from Table 1, the implementations, one to six and the comparative examples one to two show that the halogen-free flame-retardant epoxy resin composition of the present invention (the towel of the poly-p-acid-acid U• phenyl vinegar and stupid ethylene-Malay The ratio of the anhydride copolymer is 2 4: 1 to 4 0 ·· 1) The laminated board is made to meet the specifications of the printed circuit board, especially in the case of the first one, the fifth and the sixth. The resulting drop has a significant reduction effect.实实四和实关六 denotes that the present invention contains a composite hardening 15 201139496 agent (for example, a styrene-maleic anhydride filament is further mixed with a first-class amine) The laminated board still meets the specifications required by the printed circuit board. Referring to the comparative example 1, the laminated board shown by the method has a large brittleness, is inferior in diligence, and is easy to fall when cutting, and refers to the second comparative example. 'It shows that the dip solder resistance and the tear strength dielectric constant of the laminated board produced by the laminate are deteriorated.

The present invention is applied to a non-functional epoxy resin composition by a combination of a specific ratio of a styrene-maleic anhydride copolymer and a low molecular weight t-methyl-acid 1,3_phenylene group. The prepreg material is brushed to improve the brittleness problem caused by the addition of styrene-malay g-anhydride as an epoxy resin hardener during the process of adding I, for example, in ribs and drill holes. The falling objects will increase, and at the same time, the heat-resistant characteristics or electrical characteristics such as Dk, Df, etc. of the laminated board are not affected by the addition of the flame retardant, and the flame retardant properties of the laminated board can be improved. It will be apparent to those skilled in the art that various modifications and changes can be made without departing from the spirit and scope of the invention. Therefore, the present invention includes such modifications and variations, and is included in the scope of the patent application and its equivalents.

16 201139496 [Simple description of the diagram] Benefits [Main component symbol description] None

Claims (1)

201139496 VII. Patent application scope: 1. A non-self-flame flame retardant epoxy resin composition, including: (8) 100 parts by weight of halogen-free epoxy resin (8) Ben-fine-maleic acid copolymer (^rene_Maieic aj^ydride Copolymer) as a hardener, based on 1 part by weight of the halogen-free epoxy resin, the content of the styrene-maleic anhydride copolymer is from 1 to 2 parts by weight, and the structural formula is as follows: η where m is an integer from 1 to 6, and η is an integer from 2 to 12; and (c) p〇iy (i, 3-phenylene methylphosphonate) As a flame retardant, the content of the 1,3-phenylene polymethyl phosphate is 25.0 to 70.0 parts by weight based on 100 parts by weight of the halogen-free epoxy resin, and its structural formula is as follows: (HO ), 〇II Ο a P — 〇 0 II -Ο-P-〇. I CH, (OH) mm = 0 or 1, n = 0 or 1, p is an integer, wherein the poly(triphenylphosphine) 1,3-phenylene ester has a molecular weight of less than 1000, and the polyfluorenyl phosphate The ratio of the phenyl ester to the styrene-maleic anhydride copolymer is from 2.0:1 to 4.0:1 by weight. 2. The halogen-free flame-retardant epoxy resin composition according to claim 1, wherein the poly(trimethylphenyl phosphate) 1,3-phenylene ester and the styrene-maleic anhydride copolymer are The ratio is 2.7: 1.0 by weight. 201139496 3. For the application of the halogen-free epoxy resin composition described in Item 1, wherein the halogen-free epoxy resin contains a Wei oxygen resin or a nitrogen-containing epoxy resin. 4. The halogen-free flame-retardant epoxy resin composition as described in claim 3, wherein the epoxy resin-containing compound, 9,1G·dihydrooxophosphorus 1〇_ Oxide is introduced into the squamous epoxy resin structure formed by the structure of the adjacent epoxy resin. 5. Halogen-free flame retardant as described in claim 1 The epoxy resin composition 'where' the styrene-maleic anhydride copolymer is mixed with a primary amine as a hardener. 6. A halogen-free flame-retardant epoxy resin as described in claim i. The composition $' further includes a hardening accelerator' in an amount of a halogen-free epoxy resin, and the hardening accelerator is contained in an amount of from 0.01 to 1.0 part by weight. The flame retardant epoxy resin composition of the 'in which the hardening promotes the vehicle (4), the compound. The flame retardant epoxy resin of the element described in the first item is: the machine filler '1 〇 0 weight The content of the halogen-free epoxy resin is 5 〇 to 3 〇〇 by weight of the reference two machine. 9 6 Γϋ., in - reinforcing material In the middle of the application, the scope of the application for patents No. 2, 5, and the flawless epoxy resin test substance, and the drying of the 姑 卩 卩 Μ Μ 板 系 系 系 * * * * 9 9 9 9 9 The prepreg-side ί is formed to form a laminated board, and at least one of the laminated boards is covered with two: Ϊ-gold shot "Get - metal lamella laminate, and in the genus coating layer The metal red on the surface of the board forms a certain circuit pattern and is made into 201139496. 4. The designated representative figure: (1) The representative figure of the case is: the (none) figure. (2) The symbol of the representative figure is simple: If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: